Coloured polymeric synthetic material



United States PatentO ,COLOURED POLYMERIC SYNTHETIC MATERIAL :WernerBdssard, Riehe'n near Basel, and Jacques Voltz, Basel, Switzerland, assignors to J. R. Geigy A.-G.,,

Basel, Switzerland 7 v i No Drawing. Filed Oct. 20, 1958, Ser. No. 768,055 8 Claims. (Cl. 8-55) The present invention concerns a process for the dyeing and printing of synthetic materials made up from poly-:

merisedor copolyme'rised acrylonitrile. It also concerns,

as industrial :product, the materials fast dyed according to the new process. M

It has now beenfound that colour salts, the coloured cations of which contain no carboxylic acid and sulphonic acid groups and which correspond to the general formula are excellently suitable for the idyeing and printing in pure and fast shades of polymeric synthetic mate rials, which are producedto a great extent from acrylonitrrleL;

' In the above formula Y and Y each represent a member selected from the group consisting of hydrogemlower alkyl, carbalkoxy and mononucleararyl radicals, and,

X and X each represent the divalent radical necessary to completea heterocyclic nucleus containing from 5 to 6 atomsin the heterocyclic ring.

i 'For the; rest, the formula should be read as representing not just theelectromencformula given but as embracing all electromeric possibilities; V The colour salts used according to the present mvention are diagoaminocompounds in'wvhich two heteroeyclic nitrogen-containing rings. are bound by a triaz ene grou-p =NN=N-. They are referred 'to in the followlng as triazene dyestuffs.

The anions of these'colour salts which, advantageously,

are not coloured andthereforeare' of noimportance to the dyestuff character, are derived in particular :from W strong inorganic or organic acids, if desired ,complex acids, for example from halogen hydracids, from sulphuric acid, sulphuric'acid monoallryl esters, perchloric. acid or the double salt of the chlorideof the-idyestutl wlth, zinc chloride, from strong aliphatic carboxylic acids such' as oxalic acid or lactic acid or from aromatic sulphonic "acids such as "e.g. benzene sulphonic acid1 or toluene sulphonic acids.

According to the general Formula 1' the t'riazenes used accordingt {h v present invention" contain two nitrog f containing five or six membered hetero rings. These can also be condensed "with other rings, advantageously aromatic-isocyclic rings. The radicals X and X 'are either organic divalent radicals or divalent hetero groups,

or hetero atoms. Chiefly nitrogen, oxygen and sulphur atoms are meant by hetero atoms according to the present invention. Those members of the radicals Xi and X which complete the nitrogen-containing hetero rings can consist only of carbonlatoms or of carbon and hetero atoms or of hetero atoms alone. The number of members completing the rings depends on the size of the hetero rings. The members of the radicals X which do not take part in the ring formation are substituents of the hetero ring or components of fusedrings.

Some examples are given in the following which illustrate the meanings of X and X Chiefiy thoseradicals are meant in which the members completing the nitrogencontaining hetero ringare of a purely organic nature.

For example if X is an uq-propenylene radical, then the heterocyc'lic ring. is an isopyrrole ring. An u.6-butadientaining hetero ring contains hetero atoms. For example if X is the group -CH=CHS', then it completes a thiazole ring. Correspondingly, the group,

.c ompletesan oxa zolje ring, the greu onemptincompletes an imidazole ring, the group -N CH- NH completes a triazole ring, the group -N= N-NH- completes a tetrazole ring and the group -N=CH-S completes a thiadiazole ring. If, in the triazene compounds used according to the present invention the nitrogen-containing heterocycles arecondensed with other 7 rings, then these are advantageouslyarornatic-isocyclic' rings. Examples are-the benzimidazole, indazole, benzoxazole, benzthiazole and naphthothiazole rings. These rigns are linked to the triazene group when X represents anxanilino, phenoxy, phenylthio or naphthylthio radical I bound at the hetero atom and in o-position thereto.

The organic radicals bound at thein'ng nitrogen atoms, and represented in the general Formula lby C H -Y and C H Y are chiefly of an araliphatic or aliphatic nature; advantageously they are benzyl and alkyl' groups which may possibly; be substituted. Also,"'Y and Y can becarbalkoxy radicals such as e.g.' the carbomethoxy or carbethoxy radical. The triazene-dyestuffs used according to the present invention can otherwisebe subs;

tuted as desired except by acid dissociating groups. The

substituents may be, in particular, those usual in azo dyestuffs, for example halogens, cyano, "alkyl, alkoxy,

alkylarnino, alkyl'sulphonyl, carboxylic acid and sulplionic acid ester and amide groups. I r Preferred dyestuffs usable according to the present invention are" those in which the symbols -CH Y and GH -"Y in the general formula represent'low' molecular alkyl'groups. For technical and economic reasons they arelin particular methyl and ethyl groups. Dye stuifs in which the"nitrogen-containinghetero rings are Patented Apr. 4, 1961 i 3 of aromatic character and have five members are particularly preferred.

Of these preferred triazene dyestulfs, those are particularly preferred in which at least one hetero ring is an azole ring, chiefly a pyrazole, imidazole, triazole, tetrazole, thiazole, thiadiazole or oxazole ring, and this azole ring is advantageously bound with a benzo radical which may possibly be substituted such as for example in the benzimidazole, indazolefbenzthiazole and benzoxazole rings. Finally, triazene compoundsuin which-both hetero rings are azole rings of the preferred type, are a valuable class of dyestuffs within the scope of the present invention. a 1 a Particularly valuable and therefore preferred are the benzthiazole triazene dyestuffs.

The triazenes used according to the present invention can be produced for example in the following manner: a heterocyclic amine of the general formula eral Formula II with an imino compound of the general formula wherein X has the meaning given above and Y has that of Y or Y and alkylating the coupling product. The imino compounds can be produced for example from 'heterocyclic amines of the general Formula II with alkylating agents. A third method of producing the triazenedyestuffsused according to the present invention consistsin condensing a heterocyclic' amine of the general Formula II with a nitroso imine which is obtained by treating an imine of? the general Formula III with nitrous acid." The condensation product is then converted into the cyclammonium compound. This is doneb'y treating it for example with estersof low alcohols and halogen hydracids, sulphuric acid or aromatic sulphonic' acids. Triaiene compounds in which the two radicals Y and Y are dif-:

ferent from each other can be produced by the second and third processes. p

In the process according to the present invention, triazene dyestuffs containing cyclammonium groups are used advantageously as salts of strong inorganic or organic acids, in particular 'as chlorides or bromides, double salts of the dyestufl hydrochloride and ziric'chloride, as perchlorates or methyl sulphates, as benzene sulphonates or p-methyl benzene sulphonates; In these forms they dissolve in water with a more or less neutral reaction and dye fibres of polymeric or copolymeric synthetic, materials which are produced to agreat extent from acrylonitrile in weakly acid, neutral to weakly for example benzoic acid, o-phenylphenol, salicylic acid ester, S-cyanoethyl formamide and fl-cyanoethyl benzamide, which cause an improvement in the drawing power of the dyestuffs. It is sometimes of advantage to add retarding agents to the dye baths. With mixtures of different dyestuffs or of different types of dyestuffs such as are necessary for example for the dyeing of mixed fabrics as well as for the attainment of fashionable shades, these retarding agents cause the dyestufis to draw evenly onto the fibres with good exhaustion of the bath. For example, organic polysulphonic acids, possibly in the presence of a fatty alcohol polyglycol ether acting as a dispersing agent can be used as such retarding agents. Apart from dyeing from an aqueous bath, the triazene dyestuffs used according to the present invention can also be used for the printing of polymeric or copolymeric acrylonitrile fabrics or foils.

Fibres consisting of polymeric or copolymeric synthetic materials which are produced to a great extent from acrylonitrile and are intended as goods to be dyed in the present process are, for example, the marketed products Crylor? of the Socit Rhodiaceta S.A., Lyons (France), Dralon" of Farbenfabriken Bayer A.G., Dormagen (North Rhineland-Westphalia), Orlon 42" of E. I. du Pont de Nemours & Co. Inc., Wilmington, Delaware (U.S.A.), Nyrncrylon of N.V. Kunstzijdespinnerij, Nyma, Nijinegcn (Holland) and Wolcrylon" of VEB Filmand Chemiefaserwerk AGFA-Wolfen, Wolfen (Bitterfeld region). 7

Pure yellow to red dyeings are obtained with the triazene dyestuffs used according to the present invention on fibres or fabrics made up from polyacrylonitrile such as, for example, Orlon 42. On dyeing mixed fabrics made up from acrylonitrile polymers and wool, the latter is practically completely reserved. That these triazene compounds could be used for attaining technically valuable dyeings could not have been foreseen as usually triazene compounds are instable in acid solution at a raised temperature and split into the corresponding diazonium and amino compounds. The stability of the triazene compounds claimed, even in mineral acid, boiling aqueous solutions is, therefore, all the more surprising. The dyeings obtained with these compounds on fibres made up of polyacrylonitrile are distinguished also by surprisingly good fastness to Washing, milling, ironing and pleating. Also, in contrast to other diazoamino compounds, some of the claimed triazene compounds have really excellent fastness to light on polyacrylonitrile fibres which a is all the more remarkable as the triazene compound according to the present invention decompose extraordinarily easily on exposure to light. The new dyestuffs have excellent leveling powers and fasteness to cross dyeing.

Further details-can be seen from the following examples which serve to illustrate the invention without limiting it in any way. Where not otherwise stated, in the examples parts are given as parts by weight and the temperatures are in'degrees centigrade. The relationship alkaline baths at a raised temperature. 'The fibres or textiles made up therefrom are dyed advantageously in an acetic acid, formic acid or sulphuric acid bath in'a pH range which can vary between, for example, 2T0 6.

Dyeing is performedadvantageously at the boil, possibly under pressure and if necessary in the presence of leveling agents, wetting agents andother dyeing additives.

The so-called carriers, among others, are such additives,

of parts by weight to parts by volume is as that of kilogrammes to litres.

, 7 Example 1 1 0.5 parts of the dyestuff a s s i V Y V Cl-ZnCl: l N I V 3H: 7

are pastedwith 0.5 parts of acetic acid and dissolved in 4000 parts of hot water. 1.0 part of 80% acetic acid,.2 parts of sodium acetate and 4 parts of a condensation product from olein alcoholandl5 mol of ethylene oxide are added. The pH of this solution is Orlon 42 fibre which has been dyed in vidid orange "ethylatingwith?diethylsu1phat6 I a I '5 a t about 4.5. At 5O, 100 parts of "Orlon 42 (polyacrylonitrile fibre of du Pont, Wilmington, Delaware U.S.A.) are entered, the temperature is raised within 15 minutes to 100 and dyeingis performed for one hour at the boil. The dyebath is almost completely exhausted after this time. The dyed goods are saponified at 80 for 15 minutes in 5000 parts of water with Sparts of a fatty alcohol sulphonate and then rinsed and dried. The

shades has excellent fastness to washing and light.

The dyestutf used is obtained by condensing Z-nitrosoimino-3-methyl 2,3 dihydrobenzthiazole andZ-amino- 'benzthiazole in glacial acetic acid and then methylating I in dirnethyl sulphate at 100-110. I I I I It is isolated by taking up the met-hylation product in water and precipitating the colour saltwith zinc; chloride and sodium chloride. 7

I on 01 action product is precipitated with 6. Example 3 0.5 parts of the dyestulf s\ s CHiO CN=NN=C 01-21101, I

\ 7/ I I?/ on. on:

are pasted with 0.5 parts of 80% acetic acid and then dissolved in 4000 partsof water. acetate, 1 part of 80% acetic acid and 4 parts of a condensation product from olein alcohol and 15 mols of ethylene oxide are added to this solution. I 100 parts of Dralon (polyacrylonitrile fibre of Farbenfabriken Bayer A.G., Dormagen, North Rhineland-Wes'tphalia, Germany) are entered, the temperature of the bath is raised to 90 within 30 minutes and kept at this temperature for 10 minutes and then dyeing is performed at the boil for 1 hour. The dye bath is exhausted to a great extent. The dyed goods are thoroughly saponified, washed anddried. A pure red-orange Dralon fibre dyeing is obtained which has excellent fastness to light and washing. 1 v

The dyestutf used above is obtained by methylating the coupling product of G-methoXy-benzthiazolyl-2- diazonium sulphate and Z-amino-benzthi'azole. The re zinc chloride and sodium chloride from aqueous solution. I 1

Further colour salts having similardyeing properties are given in the following table. The products are obtained by coupling component B with the diazoniurn salt from amine A and then alkylating with C. I

' I I Shade on poly- No. A B O acrylonitrile fibre 1 2-a)mino t i-me thoxy- 2-amino-benzthiazo1e diethylsulphatel scarlet. ggij fii 2-amino-fi-methylbenzthiazole p-toluene sulphonic acid redorange.

- methyl ester.

2-aniino-6-methoxybenzthidimethyl sulphate rust red.

do B-bromaceticacidmethylester. Do.

. z chlorethyl ester.

'2-amino-fi-chlorobenzthlazoledimethyl sulphate red-orange.

3-amino-indazo'ledo I orange.

2-amino-pyrazole 'd0 Do.

2-amino-4-methyl thiazole n-butyl iodide yellow-orange. 2-amino-4.5-diethy1thiazole. p-toluenesulphom'caeidethyl Do.

S l'. do bei1Zlbf0mlde Do.

. then dyeing is performed at the boil for 30 minutes? The. U I I I Example 4y I 'dyed'goods are saponified, rinsed and dried. A .Crylon fibre dyed in vidid yellow-orange shades is obtained 0.5 parts of the dyestuff' V which has excellent fastness to washing and light; I I I a t I S r I I I c y ag dyed similarly and with the same properties I I II I y is obtained if dyeingis performed ata higher pHvalue. I N -N C I YDCI I If for example the goods are entered at 40 into a bath 7 \II I H 1 B Y which contains 0.5 parts of dyestufi, 4 part's of a con-' I densation product from olein alcohol and 15 mol of eth- I 7 C V ylene oxide and 1 part of crystallised sodium carbonate I I CH3 I t water the H value of the bath being t a r h l sgu 0 z nc ltlfe temperatur israised to 9,5l00-with m used 9 (polyacrylomtrllefibm Du in 15 minutes and dyeing is performed for 30 minutes l f lf l Ei' T d q g at the boil, then after saponifying. rinsing and drying, i i g P e e 8 S are Y6 111 pure h similarly and'fast dyedfibre is'obtained. a 5- p g d bta; d b on En I Similar results are Obtained-Od'dyeing. at a lower Y? I 15 0 I Y P H range for exampleon adding dilutedshydroc'hloric l f a t -Q W 3} -lmlno 3 methcidor slilphuric acid to the dyestuif solution-and dye Y1 benzthlazplme and then y gy l CBSS dllnething at a pH value 01: 3. In'all three cases-the dyeings sullihmm h pfi QQ Q have the same shades and the same good properties. Dyemfgs on polyacrylomlnle 511701.13? pfopirties I Thedyestulfused in the above process is obtained by I a obtfamed under the SaHIIE xcondltlcms 011 1181118 the y coupling benithiazolyl-Z-diazonium. sulph ate, with 2- fi lf m the o l s f imino-3-methyl-2.3-dihydrothiodiazole-(113.4) and then rare Obtallled byfi l p g e l tlsed am ne Wlth I I .75 the coupling component B and then alkylating with C.

2 parts of sodium v Shade on poly- No. A l3 7 O acrylonitrlle' fibre -a(min4o)triazole- 2-imino-3-methylthiazoline-.. n-butyliodidm; yellow. 7 3 a 1.2.

do B-bromacetleacid butylester jDoL 2 -in11iino 3.4.5 -trimethylthiadimethyl sulphate Do.

zo ne. 2-imino-3.6-dimethylbenzdo Do.

thiazoline.

2 imino 3 methyl 6 methp-toluene sulphonie acid ethyl yellow-orange.

oxy-benzthiazoliue. ester. 2 -imino u methyl 6 ehlorop-toluene sulphonic acid-flyellow. v

benzthiazoline. V ehlorethyl ester. 2-iu1i no-3.6-dimethylbenzthia- B-bromacetie acid ethyl ester Do.

2 me. 2-imino-3-methylthiazoline..- beuzylbromide v Do. 1.3 dimethyl 2 iminobeuzdimethyl sulphate Do.

imidazoliue. 3-amino-indazole diethyl sulphate Do. 3-amino-pyrazole dimethyl sulphate Do. Y

2-arnino-thiodiazole-(L3A) do Do. Z-aminoqninnlino diethyl snln'hato Do Example 5 whereln 100 parts of D l l it il fib Pal-hem Y and Y each represent a member selected from the fabriken Bayer A.G. Dormagen, North Rhineland-Westgr up conslst ug of hydrogen, lower alkyl, carbalkoxy phalia, Germany) are treated as described in- Example 3 and mononucleaf afY1IadiCa1S, and with 05 parts f the colour salt X and X each represent the divalent radical necessary to complete a heterocyclic nucleus selected from the CH: group consisting of nuclei of the benzthiazole, thiazole,

indazole, pyrazole, triaz'ole, benzimidazole, thiodiazole,

s HO 0H quinoline and pyridine series and the corresponding g 2,3-d1hydronucle1.

V 2. A composition of matter consisting of polymeric (lmI5 (E2115 S03 and copolymeric synthetic materials in form of fibres and threads, which consist chiefly of polyacrylonitrile and of a colour salt the cation of which contains no whereupon yellow-orange dyeings having very goodfastsulpho and carboxyl groups and which corresponds to ness to light and washing are obtained.

the eneral formula The colour salt used is obtained by ethylating the g coupling product of thiazolyl-Z-diazonium sulphate and 7 X1\ 7 /X: 2-imino-3-ethyl thiazoline with p-toluene sulphonic acid ;N ethyl ester." The dyestufls given in the following table N have similar behaviour. They are obtained by coupling t V ,l y 7 7 the diazotised amine A with the coupling component B 1 2 and then alkylating with C. t t I l Y1 is 7 p 7 Shade on poly- No. A B O A aerylonitrlle fibre l 2-aminothiazole--. 2-imino-3-methyl-thiazoliuen-butyl iodide yellow-orange; 2 2amino-4-methyl do benzyl bromide Do. thiazole. 3 2 amluo-thiazole 2-imino-3.6-di1uethyl-benz- Do. 7

- thiazoline. V p 4 do Z-imiuo-3-methyl-6-methoxydimethylsulphate orange.

benzthiazoline. 5 ..do 2-imino-1-methyl-pyridine..-- ptoluenesulphonicacidethyl yellow,

es-er. t 6 ..do 1-3-dimethyl-2-i mino-benzirnidimethyl sulphate; Do.

dazoline. r 7 do 3-amino-indazo1e do f Do. 8 do 2-imino-3.6-di.methyl-benzfl-bromacetic acid ethyl ester Do.- thiazoline. j

What we claim is: l. A composition of matter consisting of polymeric wherein and copolymeric synthetic materials in form of fibers and threads, which consist chiefly of polyacrylonitrile and of a colour salt the'cation of which contains no sulpho and carboxyl groups and which corresponds to Y and Y each represent a member selected from the group consisting of hydrogen'and lower alkyl radicals,

the general formula and l 1 I 1 X and X each represent the divalent radical necessary X to complete -a thiazole nucleus. .7 t

C-N=NN=C 1 7 1 N 3. A composition of matter consisting of polymeric 1 U and copolymeric synthetic materials in form of'fibers (3H1 and threads, which consist chiefly of polyacrylonitrile and Y1 Y2 of a colour salt the cationofwhich contains no sulpho and carboxyl groups and which corresponds to the general formula wherein Y and Y eachrepresent a member selected fromthe group consisting of hydrogen and methyl and X and X each represent the divalent-radical necessary to complete a benzthiazole nucleus.

4. A composition of matter consisting of polymeric and copolymeric synthetic materials in form of fibers and threads, which consist chiefly of polyacrylonitrile and of a colour salt of the formula v 5. A composition of matter consisting of polymeric and copolyrneric synthetic materials in form of fibers and threads, which consist chiefly of polyacrylonitrile and of a colour salt of the formula 6. A composition of matter consisting of polymeric and copolymeric synthetic materials in form of fibers and threads, which consist chiefly of polyacrylonitrile and of a colour salt of the formula CH3 CH 8. A composition of matter consisting of polymeric and copolymeric synthetic materials in form of fibers and threads, which consist chiefly of polyacrylonitrile and of a colour salt of the formula References Cited in the file of this patent UNITED STATES PATENTS 2,832,764 Huenig a Apr. 29, 1958 

1. A COMPOSITION OF MATTER CONSISTING OF POLYMERIC AND COPOLYMERIC SYNTHETIC MATERIALS IN FORM OF FIBERS AND THREADS, WHICH CONSIST CHIEFLY OF POLYACRYLONITRILE AND OF A COLOUR SALT THE CATION OF WHICH CONTAINS NO SULPHO AND CARBOXYL GROUPS AND WHICH CORRESPONDS TO THE GENERAL FORMULA 